Origin of organic compounds in carbonaceous chondrites.

Carbonaceous chondrites, a class of primitive meteorite, have long been known to contain their complement of carbon largely in the form of organic, i.e., hydrocarbon-related, matter. Both discrete organic compounds and an insoluble, macromolecular material are present. Several characteristics of these materials provide evidence for their abiotic origin. The principal formation hypotheses have invoked chemistry occurring either in the solar nebula or on the parent body. However, recent stable isotope analyses of the meteorite carboxylic acids and amino acids indicate that they may be related to interstellar cloud compounds. These results suggest a formation scheme in which interstellar compounds were incorporated into the parent body and subsequently converted to the present suite of meteorite organics by the hydrothermal process believed to have formed the clay minerals of the meteorite matrix.     

The chemical conditions on the parent body of the murchison meteorite: Some conclusions based on amino, hydroxy and dicarboxylic acids

Amino and hydroxy acids have been identified in the Murchison meteorite. Their presence is consistent with a synthetic pathway involving aldehydes, hydrogen cyanide and ammonia in an aqueous environment (Strecker-cyanohydrin synthesis). From the various equilibrium and rate constants involved in this synthesis, four independent estimates of the ammonium ion concentrations on the parent body at the time of compound synthesis are obtained; all values are about 2 × 10^?3 M. Succinic acid and β-alanine have also been detected in the Murchison meteorite. Their presence is consistent with a synthesis from acrylonitrile, hydrogen cyanide and ammonia. Using the equilibrium and rate constants for this synthetic pathway, and the succinic acid/β-alanine ratio measured in the Murchison meteorite, an estimate of the hydrogen cyanide concentration of 10^?3 to 10^?2 M is obtained. Since hydrogen cyanide hydrolyzes relatively rapidly in an aqueous environment ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{< 10}{}^4\text{yrs}$) this high concentration implies a period of synthesis of organic compounds as short as 10⁴ years on the Murchison meteorite parent body.     

Amino acids in meteorites.

Carbonaceous chondrites carry a record of chemical evolution that is unparalleled among presently accessible natural materials. Within the complex suite of organic compounds that characterize these meteorites, amino acids occur at a total concentration that may reach 0.6 micromole g-1 meteorite (approximately 60 ppm). Both free amino acids and acid-labile amino acid derivatives have been found in hot-water extracts of a CI1 and seven CM2 chondrites. Although the amino acid composition of all CM2 chondrites is not the same, differences may be largely explicable on the basis of spontaneous and biologically-caused decomposition occurring during their terrestrial residence. The amino acids of the Murchison meteorite (CM2) have been extensively analyzed and 52 amino acids have been positively identified. Thirty three of these amino acids are unknown in natural materials other than carbonaceous chondrites. Thus the Murchison meteorite has recently been the major source of new naturally-occurring amino acids. The Murchison amino acids comprise a mixture of C2 through C8 cyclic and acyclic monoamino alkanoic and alkandioic acids of nearly complete structural diversity. Within the acyclic monoamino alkanoic acid series, primary alpha-amino alpha-branched amino acids are predominant. The concentrations of individual amino acids decline exponentially with increasing carbon number within homologous series. Amino acid enantiomers are found in approximately equal amounts. Eight of the terrestrial protein amino acids have been found.     

Origins of amino acids in the early solar system.

Synthesis of meteoritic amino acids probably took place in the aqueous sub-surface regions of one or more asteroid-sized parent bodies. Starting material for those reactions apparently consisted of a population of more simple compounds including a suite of aliphatic precursors characterised by (1) complete structural diversity, (2) prevalence of branched- over straight-chain species, (3) exponential decrease in abundance with increasing C number, (4) large enrichment in D, and, probably, (5) systematic decrease in 13C/12C with increasing C number. Those properties were apparently acquired during synthesis of the precursors by ion-molecule reactions in a presolar molecular cloud.     

Stable isotope analysis at the molecular level: a new approach for determining the origins of amino acids in the Murchison meteorite.

A combined gas chromatography/isotope ratio mass spectrometry (GC/IRMS) method has been developed that permits the direct stable carbon isotope analysis of N(O)-trifluoroacetyl-isopropyl esters of individual amino acids and their respective enantiomers at nanomole abundances. Calculation of the original delta 13C values of the amino acids is accomplished via a correction for the carbon introduced during the derivatization process. Previous GC/IRMS analyses of individual amino acids in the non-hydrolyzed water extract of an interior sample of a Murchison meteorite stone revealed an enrichment in 13C relative to terrestrial organic matter, in agreement with previous findings for bulk extracts. The range of amino acid delta 13C values (+5 to +30%, PDB) suggests possible kinetic effects during synthesis. In this study, an apparent kinetic isotope effect was also observed for the amino acid products of a spark discharge experiment. These preliminary results are supportive of a similar mechanism for the abiotic synthesis of amino acids in the Murchison meteorite.     

吉林陨石的形成和演化过程

在对吉林陨石进行多学科综合研究所取得的成果基础上,我们对吉林陨石的形成演化过程作了如下讨论:(1)太阳星云的凝聚过程:根据吉林陨石的凝聚和固化年龄和矿物的组合,探讨了太阳星云凝聚的过程;(2)吉林陨石母体的热变质过程:从稀有气体的丢失,全岩化学成分的特征,稀土元素的自纯化过程和橄榄石、斜方辉石成分的稳定性,讨论了热变质过程的特征;(3)吉林陨石母体的冷却过程:根据镍纹石的镍含量和宽度,还根据矿物中Ar和裂变径迹的保存性,分析了吉林陨石母体的冷却史;(4)吉林陨石母体的破碎和宇宙线照射历史:根据对宇宙成因He3、Ne20,21,22、Ar38、Na22、Al26、Mn54、Mn53和Co60的测定结果,提出了吉林陨石的两阶段照射历史的模式。第一阶段的吉林陨石母体,年龄10—11my,r=10m,确定了各样品在母体中的相对位置;第二阶段的吉林陨石母体,年龄0.3—0.5my,r=80—90cm确定了各样品的埋藏深度及通过大气层后的烧失量;(5)吉林陨石的降落过程:讨论了吉林陨星在太阳系空间和大气层中的轨道及降落过程。      

Survivability of biomolecules during extraterrestrial delivery: new results on pyrolysis of amino acids and poly-amino acids.

The hypothesis on exogenous origin of organic matter on the early Earth is strongly supported by the detection of a large variety of organic compounds (including amino acids and nucleobases) in carbonaceous chondrites. Whether such complex species can be successively delivered by other space bodies (comets, asteroids and interplanetary dust particles) is unclear and depends primarily on capability of the biomolecules to survive high temperatures during atmospheric deceleration and impacts to the terrestrial surface. Recent simulation experiments on amino acid and nucleic acid base pyrolysis under oxygen-free atmosphere demonstrated that simple representatives of these (considered thermally unstable) compounds can survive at 1-10% level a rapid heating at 500-600 degrees C. In the present work, we report on new data on the pyrolysis of amino acids and their homopolymers and discuss implications of their thermal behavior for extraterrestrial delivery.     

吉林陨石稀有气体的分布特征及其热历史的初步探讨

吉林陨石的宇成和放射成因稀有气体存在大幅度的变化.宇成3He、20, 21, 22Ne和38Ar_c之间彼此近似线性相关, 放射成因4He和40Ar之间近似线性相关.放射成因4He、40Ar与作为陨星深度标尺的宇成60Co间近似线性相关, 但与作为吉林陨石母体深度标尺的21Ne之间不存在线性相关.上述事实表明:4He和40Ar在吉林陨石中的分布是不均匀的, 在吉林母体中的分布是不规则的, 而在吉林流星中, 由表面至中心呈现递增的倾向.我们试图用吉林陨石母体与小行星间的碰撞效应解释用4He和40Ar的上述独特分布特征.      

The Kumtag meteorite strewn field

The Kumtag meteorite strewn field was found in the Kumtag desert, 132 km south of Hami city in the Xinjiang province, China. It is an ellipse of 2.5 × 7.9 km, with a long axis extending along the northeast-southwest direction. The largest individual meteorite of the strewn field weighs about 10 kg; the smallest individual has a mass of only 27 g. In total, more than 100 individuals with a total mass of more than 180 kg were collected. The location and the distribution of the fragments suggest that the Kumtag meteoroid entered the atmosphere in the direction Northeast-Southwest. All meteorites collected in this strewn field are samples from the same unique meteorite shower. The Kumtag meteorite is an H5 ordinary chondrite with a shock stage S2, and a weathering grade W2. The cosmic ray exposure age of Kumtag is 6.7 ± 0.8 Ma, which is rather typical for H chondrites and which indicates that Kumtag was derived from the massive impact event on its parent body ~7 Ma ago. A significant amount of He has been lost during certain unknown processe(s) before the Kumtag meteorite was ejected from its parent body.     

Prebiotic syntheses of purines and pyrimidines

The work done in many laboratories during the last two decades has confirmed that hydrogen cyanide and cyanoacetylene are the two major precursors for the prebiotic synthesis of purines and pyrimidines, respectively. Although several different pathways for the synthesis of purines have been described, they are all variations of the initial mechanism proposed by Oró and Kimball, where hydrogen cyanide leads first to the formation of a 4,5-disubstituted imidazole derivative, and then to the closing of the purine ring with a C₁ compound. A number of experiments have shown that purines and pyrimidines can also be obtained from methane, ammonia (nitrogen), and water mixtures, provided an activating source of energy (radiation, electric discharges, etc.) is available. However, in this case the yields are lower by about two orders of magnitude because of the intermediate formation of hydrogen cyanide and cyanoacetylene. The latter two compounds have been found in interstellar space, Titan and other bodies of the solar system. They were probably present in the primordial parent bodies from the solar nebula in concentrations of 10⁻² to 10⁻³ M as inferred from recent calculations by Miller and coworkers obtained for the Murchison meteorite. These concentrations should have been sufficient to generate relatively large amounts of purine and pyrimidine bases on the primitive Earth.     

A novel way for the formation of alpha-amino acids and their derivatives in an aqueous medium.

In the course of a study of possible mechanism for chemical evolution in the primeval sea, we observed the formation of alpha-amino acids and N-acylamino acids from alpha-oxo acids and ammonia in an aqueous medium. Glyoxylic acid reacted with ammonia to form N-oxalylglycine, which gave glycine in a 5-39% yield after hydrolysis with 6N HCl. Similarly when glyoxylic acid was treated with methylamine it yielded N-oxalylsarcosine, which could be hydrolyzed to sarcosine with 17-25% overall yield upon hydrolysis. Pyruvic acid and ammonia reacted to give N-acetylalanine, which formed alanine in a 3-7% overall yield upon hydrolysis. The pH optima in these reactions were pH 3-4. These reactions were further extended to the formation of other amino acids. Glutamic acid, phenylalanine and serine were formed from alpha-ketoglutaric acid, phenylpyruvic acid and hydroxypyruvic acid, respectively, under similar conditions. N-Succinylglutamic acid was obtained as an intermediate for glutamic acid synthesis. Phenylacetylphenylalanineamide was also isolated as an intermediate for phenylalanine synthesis. Alanine, rather than aspartic acid, was produced from oxaloacetic acid. These reactions provide a novel route for the prebiotic synthesis of amino acids. A mechanism for the reactions is proposed.     

吉林陨石的熔融实验研究及其在地球化学中的应用

组成地球的初始物质很可能是IAB铁陨石及H群球粒陨石,非均匀吸积形成地球以后,除由岩浆分异作用使幔中金属-硫化物下沉到原始地核外,在还原条件下还有部分Fe是由橄榄石中的FeO还原为Fe0而提供的并加入于地核内.对于大的陨石母体,由于内部加热或其表面受冲击加热而发生熔融和岩浆分异,导致形成某些铁陨石及无球粒陨石或7型岩石类型的球粒岩石.实验产物中的Fe-Ni-S相可作为判别宇宙球粒的标志之一.      

Direct interaction between amino acids and nucleotides as a possible physicochemical basis for the origin of the genetic code.

A study of the association of homocodonic amino acids and selected heterocodonic amino acids with selected nucleotides in aqueous solution was undertaken to examine a possible physical basis for the origin of codon assignments. These interactions were studied using 1H nuclear magnetic resonance spectroscopy (NMR). Association constants for the various interactions were determined by fitting the changes in the chemical shifts of the anomeric and ring protons of the nucleoside moieties as a function of amino acid concentration to an isotherm which described the binding interaction. The strongest association of all homocodonic amino acids were with their respective anticodonic nucleotide sequences. The strength of association was seen to increase with increase in the chain length of the anticodonic nucleotide. The association of these amino acids with different phosphate esters of nucleotides suggests that a definite isomeric structure is required for association with a specified amino acid; the 5'-mononucleotides and (3'-5')-linked dinucleotides are the favored geometries for strong associations. Use of heterocodonic amino acids and nonprotein amino acids supports these findings. We conclude that there is at least a physicochemical, anticodonic contribution to the origin of the genetic code.     

Self-instructed condensation of amino acids into polymers

In contemporary cells biological information is largely stored in nucleic acids. Therefore, a prerequisite in many theories on the origin of cellular life is the pre-existance of self-replicating polynucleotides that had to be formed by abiotic processes on the prebiotic Earth. It is usually assumed that the spontaneous synthesis of a self-replicating polynucleotide could take place readily. However, serious stereochemical obstacles exist which make such a synthesis extremely improbable. Amino acids on the other hand, which are abundantly formed in prebiotic simulation experiments, are relatively easily polymerized to macromolecules (protoproteins) that share with modern proteins many properties: e.g., definable non-random structure, selected amino acid sequences, enzyme-like activities and self-assembly into supramolecular structures. Prebiotic polyamino acids are therefore regarded by some scientists, including the present author, as the first informational macromolecules. The origin of this information is the chemical reactivity of the various prebiotic amino acids and their chemical response to their environment. The first informational polynucleotides were likely formed by a polynucleotide polymerase activity of prebiotic protoproteins. A contemporary model for this process is seen, e.g., in the activity of template-free Qβ-replicase.     

Chemical evolution of primitive solar system bodies.

In this paper we summarize some of the most salient observations made recently on the organic molecules and other compounds of the biogenic elements present in the interstellar medium and in the primitive bodies of the solar system. They include the discovery of the first phosphorus molecular species in dense interstellar clouds, the presence of complex organic ions in the dust and gas phase of Halley's coma, the finding of unusual, probably presolar, deuterium-hydrogen ratios in the amino acids of carbonaceous chondrites, and new developments on the chemical evolution of Titan, the primitive Earth, and early Mars. Some of the outstanding problems concerning the synthesis of organic molecules on different cosmic bodies are also discussed from an exobiological perspective.     

Formation of oligopeptides on the surface of small bodies in solar system by cosmic radiation.

The present experiment indicates that oligopeptides are easily produced in solid state from mixtures of simple amino acids by irradiating with high energy charged particles. We investigated such amino acids and their mixtures as tryptophan, tyrosine and glycine. The thin films was irradiated with protons (6.6 MeV). Such dipeptides as Trp-Trp, Gly-Tyr, Tyr-Gly, and Tyr-Tyr have been detected as products of irradiation. Cosmic rays might be an effective energy source for abiotic formation of bioorganic compounds on the surface of small bodies in the solar system on early stage of formation of planets as well as at present day.     

吉林陨石（H5）的冲击压缩线及其意义

在二级轻气炮动高压装置上运用电探针技术测量了具有H群球粒陨石典型代表性的吉林陨石冲击压缩线。当冲击压力>～70GPa时,吉林陨石发生相变,其高压相零压密度为4.425g/cm~3,硅酸盐部分高压相零压密度为4.068g/cm~3。吉林陨石冲击压缩性质的研究结果与地球形成的星子堆积模型(IAB铁陨石+H群球粒陨石)一致。此外,根据陨石或其类似物的冲击压缩线,用阻抗匹配原理计算了主要类型陨石中重要冲击特征形成的最小碰撞速度,揭示了陨石冲击效应形成的动力学条件与空间环境。     

Formation of amino acid precursors in cometary ice environments by cosmic radiation.

Cometary ices are believed to contain water, carbon monoxide, methane and ammonia, and are possible sites for the formation and preservation of organic compounds relating to the origin of life. Cosmic rays, together with ultraviolet light, are among the most effective energy sources for the formation of organic compounds in space. In order to study the possibility of the formation of amino acids in comets or their precursory bodies (interstellar dust grains), several types of ice mixtures made in a cryostat at 10 K ("simulated cometary ices") were irradiated with high energy protons. After irradiation, the volatile products were analyzed with a quadrupole mass spectrometer, while temperature of the cryostat was raised to room temperature. The non-volatile products remaining in the cryostat at room temperature were collected with water. They were acid-hydrolyzed, and analyzed by ion-exchange chromatography. When an ice mixture of carbon monoxide (or methane), ammonia and water was irradiated, some hydrocarbons were formed, and amino acids such as glycine and alanine were detected in the hydrolyzate. These results suggest the possible formation of "amino acid precursors" (compounds yielding amino acids after hydrolysis) in interstellar dust grains by cosmic radiation. We previously reported that amino acid precursors were formed when simulated primitive planetary atmospheres were irradiated with cosmic ray particles. It will be of great interest to compare the amount of bioorganic compounds that were formed in the primitive earth and that brought by comets to the earth.     

Chemical evolution of RNA under hydrothermal conditions and the role of thermal copolymers of amino acids for the prebiotic degradation and formation of RNA.

The roles of thermal copolymers of amino acids (TCAA) were studied for the prebiotic degradation of RNA. A weak catalytic ability of TCAA consisted of Glu, L-Ala, L-Val, L-Glu, L-Asp, and optionally L-His was detected for the cleavage of the ribose phosphodiester bond of a tetranucleotide (5'-dCrCdGdG) in aqueous solution at 80 degees C. The rate constants of the disappearance of 5'-dCrCdGdG were determined in aqueous solutions using different pH buffer and TCAA. The degradation rates were enhanced 1.3-3.0 times in the presence of TCAA at pH 7.5 and 8.0 at 80 degrees C, while the hydrolysis of oligoguanylate (oligo(G)) was accelerated about 1.6 times at pH 8.0. A weak inhibitory activity for the cleavage of oligo(G) was detected in the presence of 0.055 M TCAA-Std. On the other hand, our recent study on the influences of TCAA for the template-directed reaction of oligo(G) on a polycytidylic acid template showed that TCAA has an acceleration activity for the degradation of the activated nucleotide monomer and an acceleration activity for the formation of G5' ppG capped oligo(G). This series of studies suggest that efficient and selective catalytic or inhibitory activities for either the degradation or formation of RNA under hydrothermal conditions could have hardly emerged from the simple thermal condensation products of amino acids. A scenario is going to be deduced on the chemical evolution of enzymatic activities and RNA molecules concerning hydrothermal earth conditions.     

Detection of martian amino acids by chemical derivatization coupled to gas chromatography: in situ and laboratory analysis.

If there is, or ever was, life in our solar system beyond the Earth, Mars is the most likely place to search for. Future space missions will have then to take into account the detection of prebiotic molecules or molecules of biological significance such as amino acids. Techniques of analysis used for returned samples have to be very sensitive and avoid any chemical or biological contamination whereas in situ techniques have to be automated, fast and low energy consuming. Several possible methods could be used for in situ amino acid analyses on Mars, but gas chromatography would likely be the most suitable. Returned samples could be analyzed by any method in routine laboratory use such as gas chromatography, already successfully performed for analyses of organic matter including amino acids from martian meteorites. The derivatization step, which volatilizes amino acids to perform both in situ and laboratory analysis by gas chromatography, is discussed here.